Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139792
Yulu Zhang , Hangyang Feng , Weifeng Kong , Meijuan Bian , Yingying He , Qianwei Liang , Yanlong Sun , Chengzhi Zhou , Liguo Shen
A functionally graded high-entropy alloy catalyst FeCoNiCuRu0.5@nitrogen-doped carbon (FeCoNiCuRu0.5@NC) was designed to address catalytic function regulation and active-site stability challenges in peroxymonosulfate-based advanced oxidation processes. Featuring a spatially separated architecture with a RuC composite shell and a polymetallic alloy core, the catalyst suppresses transition metal dissolution, reducing ion leaching by 65.5 % versus conventional counterparts. The catalyst achieved complete carbamazepine (CBZ) removal within 30 min with a rate constant (k) of 0.460 min−1 at pH 3, and singlet oxygen (1O2) and sulfate radicals (SO4•−) were identified as the dominant active species. At pH 7, this rate constant (0.158 min−1) showed a twofold increase over that of FeCoNiCu@nitrogen-doped carbon (FeCoNiCu@NC) and a fivefold enhancement over that of Ru@ nitrogen-doped carbon (Ru@NC). The concentrations of SO4•−and 1O2 over FeCoNiCuRu0.5@NC are 1.97 and 3.38-fold higher, respectively, than those over FeCoNiCu@NC. This enhancement correlates with the superior charge transfer capability of the Ru-modified catalyst system. Remarkably, the FeCoNiCuRu0.5@NC demonstrates unprecedented pH tolerance (pH 3–11) and stability. Its dual-active-species configuration enables simultaneous degradation of electron-rich and electron-deficient pollutants, establishing a new paradigm for designing robust high-entropy alloy catalysts.
{"title":"Construction of functionally graded high-entropy alloy catalyst for peroxymonosulfate activation: Mechanism of radical/nonradical pathways","authors":"Yulu Zhang , Hangyang Feng , Weifeng Kong , Meijuan Bian , Yingying He , Qianwei Liang , Yanlong Sun , Chengzhi Zhou , Liguo Shen","doi":"10.1016/j.jcis.2025.139792","DOIUrl":"10.1016/j.jcis.2025.139792","url":null,"abstract":"<div><div>A functionally graded high-entropy alloy catalyst FeCoNiCuRu<sub>0.5</sub>@nitrogen-doped carbon (FeCoNiCuRu<sub>0.5</sub>@NC) was designed to address catalytic function regulation and active-site stability challenges in peroxymonosulfate-based advanced oxidation processes. Featuring a spatially separated architecture with a Ru<img>C composite shell and a polymetallic alloy core, the catalyst suppresses transition metal dissolution, reducing ion leaching by 65.5 % versus conventional counterparts. The catalyst achieved complete carbamazepine (CBZ) removal within 30 min with a rate constant (k) of 0.460 min<sup>−1</sup> at pH 3, and singlet oxygen (<sup>1</sup>O<sub>2</sub>) and sulfate radicals (SO<sub>4</sub><sup>•−</sup>) were identified as the dominant active species. At pH 7, this rate constant (0.158 min<sup>−1</sup>) showed a twofold increase over that of FeCoNiCu@nitrogen-doped carbon (FeCoNiCu@NC) and a fivefold enhancement over that of Ru@ nitrogen-doped carbon (Ru@NC). The concentrations of SO<sub>4</sub><sup>•−</sup>and <sup>1</sup>O<sub>2</sub> over FeCoNiCuRu<sub>0.5</sub>@NC are 1.97 and 3.38-fold higher, respectively, than those over FeCoNiCu@NC. This enhancement correlates with the superior charge transfer capability of the Ru-modified catalyst system. Remarkably, the FeCoNiCuRu<sub>0.5</sub>@NC demonstrates unprecedented pH tolerance (pH 3–11) and stability. Its dual-active-species configuration enables simultaneous degradation of electron-rich and electron-deficient pollutants, establishing a new paradigm for designing robust high-entropy alloy catalysts.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139792"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139806
Chunhui Cheng , Biluan Zhang , Lei Pang , Xiangyou Kong , Yahao Dong , Shujun Ming , Yanbing Guo , Tao Li
Hypothesis
Ammonia selective catalytic reduction (NH3-SCR) is currently constrained by a trade-off between sluggish low-temperature Cu+ reoxidation and high-temperature parasitic NH3 oxidation. We hypothesized that a dual-strategy—integrating zeolite morphology engineering with precise active site construction—could maximize isolated Cu2+ sites while suppressing CuO aggregation. This design aims to electronically couple these species to balance the reduction and oxidation half-cycles, thereby widening the operational temperature window.
Experiments
Copper-based SSZ-39 catalysts were synthesized via a heat-enhanced impregnation method on small-sized zeolite crystals with reduced thickness. Subsequent catalytic evaluations encompassed both the primary NH3-SCR and competitive ammonia oxidation (NH3-SCO) reactions to systematically decouple and map the temperature-dependent reaction pathways. To elucidate structure-activity relationships, a suite of characterization techniques, combined with density functional theory (DFT) calculations, was employed to probe the distribution, electronic structure, and synergistic reaction mechanism of the distinct copper species.
Findings
The optimized Cu4%-S39-N-HEI catalyst demonstrated exceptional performance, achieving >90 % NOx conversion at 200 °C and maintaining robust activity (> 80 %) at 500 °C, coupled with minimal N2O emissions (< 10 ppm). Mechanistic studies revealed a critical synergy: isolated Cu2+ sites function as high-affinity NH3 anchors (Ead = −2.68 eV), preventing high-temperature oxidation, while proximal CuO nanoclusters facilitate oxygen activation for low-temperature reoxidation. Theoretical calculations confirmed that electronic coupling between these species narrows the bandgap (2.51 → 2.39 eV), harmonizing the redox cycles and establishing a robust paradigm for wide-temperature efficient deNOx catalysts.
{"title":"Widening the ammonia selective catalytic reduction window over copper-based SSZ-39 zeolites: Synergy of copper(II) ions and copper oxide clusters","authors":"Chunhui Cheng , Biluan Zhang , Lei Pang , Xiangyou Kong , Yahao Dong , Shujun Ming , Yanbing Guo , Tao Li","doi":"10.1016/j.jcis.2025.139806","DOIUrl":"10.1016/j.jcis.2025.139806","url":null,"abstract":"<div><h3>Hypothesis</h3><div>Ammonia selective catalytic reduction (NH<sub>3</sub>-SCR) is currently constrained by a trade-off between sluggish low-temperature Cu<sup>+</sup> reoxidation and high-temperature parasitic NH<sub>3</sub> oxidation. We hypothesized that a dual-strategy—integrating zeolite morphology engineering with precise active site construction—could maximize isolated Cu<sup>2+</sup> sites while suppressing CuO aggregation. This design aims to electronically couple these species to balance the reduction and oxidation half-cycles, thereby widening the operational temperature window.</div></div><div><h3>Experiments</h3><div>Copper-based SSZ-39 catalysts were synthesized via a heat-enhanced impregnation method on small-sized zeolite crystals with reduced thickness. Subsequent catalytic evaluations encompassed both the primary NH<sub>3</sub>-SCR and competitive ammonia oxidation (NH<sub>3</sub>-SCO) reactions to systematically decouple and map the temperature-dependent reaction pathways. To elucidate structure-activity relationships, a suite of characterization techniques, combined with density functional theory (DFT) calculations, was employed to probe the distribution, electronic structure, and synergistic reaction mechanism of the distinct copper species.</div></div><div><h3>Findings</h3><div>The optimized Cu<sub>4%</sub>-S39-N-HEI catalyst demonstrated exceptional performance, achieving >90 % NO<sub>x</sub> conversion at 200 °C and maintaining robust activity (> 80 %) at 500 °C, coupled with minimal N<sub>2</sub>O emissions (< 10 ppm). Mechanistic studies revealed a critical synergy: isolated Cu<sup>2+</sup> sites function as high-affinity NH<sub>3</sub> anchors (E<sub>ad</sub> = −2.68 eV), preventing high-temperature oxidation, while proximal CuO nanoclusters facilitate oxygen activation for low-temperature reoxidation. Theoretical calculations confirmed that electronic coupling between these species narrows the bandgap (2.51 → 2.39 eV), harmonizing the redox cycles and establishing a robust paradigm for wide-temperature efficient deNO<sub>x</sub> catalysts.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139806"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Underwater superhydrophobic surfaces, inspired by Salvinia molesta leaves, can retain a stable air layer (plastron) that prevents wetting. However, their application in real-life maritime environments is hindered by external forces, such as hydrostatic pressure and water flow, which destabilize the plastron. Under the hypothesis that appropriately textured superhydrophobic surfaces can provide long-term plastron stability against challenging underwater conditions, superhydrophobic, hierarchically structured Poly(methyl methacrylate) (PMMA) surfaces were fabricated using plasma nanotechnology. Plastron stability was studied under external overpressures of up to 1500 mbar, simulating immersion depths of 15 m, and under continuous water flow rates up to 350 ml·min−1, corresponding to a Reynolds number of 116. Experiments were conducted in water undersaturated with air, representing a worst-case scenario more demanding than immersion in air-saturated seawater. Plastron thickness was monitored in situ using White Light Reflectance Spectroscopy (WLRS), enabling real-time tracking of air layer dynamics. The plasma micro–nanotextured PMMA surfaces presented here retained durable superhydrophobicity under high overpressures and continuous water flows for extended durations. Notably, the surfaces preserved a stable plastron under a pressure equivalent to a 10-m water depth for at least two weeks of continuous operation. Additionally, mechanisms governing plastron lifetime are analyzed in-depth, and strategies for achieving durable, long-term underwater superhydrophobicity are discussed.
{"title":"Extremely stable underwater superhydrophobicity via plasma micro-nanotexturing","authors":"Dimosthenis Ioannou , Kosmas Ellinas , Vassilios Constantoudis , Eleni Stai , Evangelos Gogolides","doi":"10.1016/j.jcis.2025.139804","DOIUrl":"10.1016/j.jcis.2025.139804","url":null,"abstract":"<div><div>Underwater superhydrophobic surfaces, inspired by <em>Salvinia molesta</em> leaves, can retain a stable air layer (plastron) that prevents wetting. However, their application in real-life maritime environments is hindered by external forces, such as hydrostatic pressure and water flow, which destabilize the plastron. Under the hypothesis that appropriately textured superhydrophobic surfaces can provide long-term plastron stability against challenging underwater conditions, superhydrophobic, hierarchically structured Poly(methyl methacrylate) (PMMA) surfaces were fabricated using plasma nanotechnology. Plastron stability was studied under external overpressures of up to 1500 mbar, simulating immersion depths of 15 m, and under continuous water flow rates up to 350 ml·min<sup>−1</sup>, corresponding to a Reynolds number of 116. Experiments were conducted in water undersaturated with air, representing a worst-case scenario more demanding than immersion in air-saturated seawater. Plastron thickness was monitored in situ using White Light Reflectance Spectroscopy (WLRS), enabling real-time tracking of air layer dynamics. The plasma micro–nanotextured PMMA surfaces presented here retained durable superhydrophobicity under high overpressures and continuous water flows for extended durations. Notably, the surfaces preserved a stable plastron under a pressure equivalent to a 10-m water depth for at least two weeks of continuous operation. Additionally, mechanisms governing plastron lifetime are analyzed in-depth, and strategies for achieving durable, long-term underwater superhydrophobicity are discussed.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139804"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139704
Priti S. Mohanty , Chi Zhang , Elisa Ballin , Francesco Brasili , Giovanni Del Monte , Emanuela Zaccarelli , Frank Scheffold
Incorporating ionic co-monomers into polymer microgels can alter their swelling behavior and introduce pH-responsiveness; however, their effect on the internal microgel structure remains poorly understood. Here we present a comprehensive study of poly(N-isopropylacrylamide-co-acrylic acid) microgels, revealing that the incorporation of ionic groups significantly alters their internal architecture. Using dynamic and static light scattering combined with small-angle X-ray scattering, we observe pronounced differences in form factors and swelling behavior between neutral and ionic microgels. These findings can be rationalized by monomer-resolved simulations, which reproduce the experimental form factors only when charge-induced alterations to the network architecture are explicitly accounted for during in silico synthesis. Our results demonstrate that electrostatic interactions modulate not only the swelling behavior but also the internal monomer density profile, highlighting the need to integrate and extend current modeling approaches for charged microgels.
{"title":"Electrostatic interactions reshape the internal architecture of ionic microgels - revision nov 2025","authors":"Priti S. Mohanty , Chi Zhang , Elisa Ballin , Francesco Brasili , Giovanni Del Monte , Emanuela Zaccarelli , Frank Scheffold","doi":"10.1016/j.jcis.2025.139704","DOIUrl":"10.1016/j.jcis.2025.139704","url":null,"abstract":"<div><div>Incorporating ionic co-monomers into polymer microgels can alter their swelling behavior and introduce pH-responsiveness; however, their effect on the internal microgel structure remains poorly understood. Here we present a comprehensive study of poly(N-isopropylacrylamide-co-acrylic acid) microgels, revealing that the incorporation of ionic groups significantly alters their internal architecture. Using dynamic and static light scattering combined with small-angle X-ray scattering, we observe pronounced differences in form factors and swelling behavior between neutral and ionic microgels. These findings can be rationalized by monomer-resolved simulations, which reproduce the experimental form factors only when charge-induced alterations to the network architecture are explicitly accounted for during in silico synthesis. Our results demonstrate that electrostatic interactions modulate not only the swelling behavior but also the internal monomer density profile, highlighting the need to integrate and extend current modeling approaches for charged microgels.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139704"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139805
Mehran Ghasemlou , Callum Stewart , Moon Paul , Samuel King , Jizhen Zhang , William Murrell , Billy J. Murdoch , Benu Adhikari , Minoo Naebe , Elena P. Ivanova , Frederick M. Pfeffer , Colin J. Barrow
Hypothesis
Colloid and interface science increasingly seeks strategies to control liquid–solid interactions through surface engineering and lubricant confinement. Biomimetic surfaces with designed lubricant-confined patterns and ultra-low adhesion to sticky fluids have garnered increased attention due to their broad applicability across numerous engineering fields. Although technologies for manufacturing silicone-based coatings are well established, the fabrication of fluorine-free slippery coatings that offer robust oil-storing capability without complex micro-texturing remains challenging.
Experiments
Inspired by frog skins, we engineered a multifunctional, self-lubricative interface decorated with random micro-sized structured wrinkles and nanochannels by simultaneous physical and chemical conjugation of vinyl-terminated polydimethylsiloxane (PDMS) with a controlled amount of low-viscosity silicone oil on starch-based bioplastics via a facile, cost-effective, and scalable process. We reasoned that the synergistic lubrication effects provided by the PDMS chains and silicone oil promoted strong swelling and integration, thereby ensuring super-lubricity.
Findings
The oil-bearing, self-lubricative coating readily slid water and other low-surface-tension liquids, resisted adhesion of multicomponent viscous fluids such as honey and tomato ketchup, delayed ice formation by up to 240 s, and showed high optical transparency (>80 %). The judicious infiltration of silicone oil into the PDMS chains resulted in low sliding angles of 10° (ethanol) and 8° (n-hexadecane) and enabled sticky honey to slide at 0.12 cm s−1 when the surface was titled at 75°. This work introduces a simple, low-cost, universal and non-fluorinated strategy to construct robust, patterned slippery coatings with liquid-like characteristics for a wide range of food-contact applications.
假设胶体和界面科学越来越多地寻求通过表面工程和润滑剂约束来控制液固相互作用的策略。仿生表面具有设计的润滑油约束图案和对粘性流体的超低附着力，由于其在许多工程领域的广泛适用性，已经引起了越来越多的关注。尽管制造硅基涂料的技术已经很成熟，但制造无氟光滑涂层，提供强大的储油能力，而不需要复杂的微纹理，仍然是一个挑战。实验：受青蛙皮肤的启发，我们设计了一个多功能、自润滑的界面，通过同时物理和化学偶联，将乙烯基端聚二甲基硅氧烷（PDMS）与控制量的低粘度硅油结合在淀粉基生物塑料上，以随机的微尺寸结构皱纹和纳米通道装饰。我们认为PDMS链和硅油提供的协同润滑作用促进了强溶胀和整合，从而保证了超润滑。研究结果：该自润滑油层易于滑动水和其他低表面张力液体，抵抗多组分粘性流体（如蜂蜜和番茄酱）的粘附，延迟结冰时间长达240 s，并表现出高光学透明度（> 80%）。将硅油明智地渗透到PDMS链中，导致10°（乙醇）和8°（正十六烷）的低滑动角，并使粘性蜂蜜在表面为75°时以0.12 cm s−1的速度滑动。这项工作介绍了一种简单、低成本、通用和无氟的策略，以构建具有液体状特性的坚固、图案光滑涂层，用于广泛的食品接触应用。
{"title":"Engineering frog-skin-inspired wrinkled self-lubricative liquid-like interfaces on biodegradable plastics","authors":"Mehran Ghasemlou , Callum Stewart , Moon Paul , Samuel King , Jizhen Zhang , William Murrell , Billy J. Murdoch , Benu Adhikari , Minoo Naebe , Elena P. Ivanova , Frederick M. Pfeffer , Colin J. Barrow","doi":"10.1016/j.jcis.2025.139805","DOIUrl":"10.1016/j.jcis.2025.139805","url":null,"abstract":"<div><h3>Hypothesis</h3><div>Colloid and interface science increasingly seeks strategies to control liquid–solid interactions through surface engineering and lubricant confinement. Biomimetic surfaces with designed lubricant-confined patterns and ultra-low adhesion to sticky fluids have garnered increased attention due to their broad applicability across numerous engineering fields. Although technologies for manufacturing silicone-based coatings are well established, the fabrication of fluorine-free slippery coatings that offer robust oil-storing capability without complex micro-texturing remains challenging.</div></div><div><h3>Experiments</h3><div>Inspired by frog skins, we engineered a multifunctional, self-lubricative interface decorated with random micro-sized structured wrinkles and nanochannels by simultaneous physical and chemical conjugation of vinyl-terminated polydimethylsiloxane (PDMS) with a controlled amount of low-viscosity silicone oil on starch-based bioplastics via a facile, cost-effective, and scalable process. We reasoned that the synergistic lubrication effects provided by the PDMS chains and silicone oil promoted strong swelling and integration, thereby ensuring super-lubricity.</div></div><div><h3>Findings</h3><div>The oil-bearing, self-lubricative coating readily slid water and other low-surface-tension liquids, resisted adhesion of multicomponent viscous fluids such as honey and tomato ketchup, delayed ice formation by up to 240 s, and showed high optical transparency (>80 %). The judicious infiltration of silicone oil into the PDMS chains resulted in low sliding angles of 10° (ethanol) and 8° (<em>n</em>-hexadecane) and enabled sticky honey to slide at 0.12 cm s<sup>−1</sup> when the surface was titled at 75°. This work introduces a simple, low-cost, universal and non-fluorinated strategy to construct robust, patterned slippery coatings with liquid-like characteristics for a wide range of food-contact applications.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139805"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139802
Xingyao Shen , Jianying Xi , Rongjie Gao, Yong Li, Jinliang Liu
Conventional photodynamic therapy (PDT) is limited by the tissue penetration depth of visible light. In contrast, traditional X-ray-induced photodynamic therapy (X-PDT) may cause collateral X-ray damage to healthy tissues. To address these challenges, this study presents an innovative heterojunction nanoplatform that produces reactive oxygen species (ROS) via dual photosensitizers upon soft X-ray excitation. The platform is built around a lanthanide-doped nanoscintillator core, NaLuF4:Tb/Gd(15 %/5 %)@NaYF4 (SNPs), which efficiently converts absorbed soft X-ray energy into visible light. The porous structure of the porphyrin-based zirconium metal-organic framework (Zr-MOF) encapsulates carbon dots (CDs) as a photosensitizer, allowing for efficient fluorescence resonance energy transfer (FRET) from SNPs to CDs through nanoscale spatial confinement. Importantly, Zr-MOF itself acts as a secondary photosensitizer, synergizing with CDs to significantly enhance ROS production. In vitro and in vivo experiments demonstrate that under low-dose soft X-ray irradiation, this platform effectively penetrates 2 cm of tissue while “cascade-amplifying” ROS generation. This enhances oxidative stress within tumor cells, inducing mitochondrial dysfunction and DNA damage. The synergistic effects promote tumor cell apoptosis and suppress breast cancer growth, demonstrating high X-PDT efficacy and biosafety. This study not only highlights the potential of combining lanthanide scintillators with metal-organic frameworks (MOFs) and CDs, but also provides a novel, highly effective, and safe therapeutic strategy for breast cancer. It overcomes the tissue penetration limitations of PDT and significantly broadens the biomedical applicability of soft X-rays.
{"title":"Cascading reactive oxygen species storm amplification via a soft X-ray-activated dual-photosensitizer nanoplatform for efficient photodynamic therapy","authors":"Xingyao Shen , Jianying Xi , Rongjie Gao, Yong Li, Jinliang Liu","doi":"10.1016/j.jcis.2025.139802","DOIUrl":"10.1016/j.jcis.2025.139802","url":null,"abstract":"<div><div>Conventional photodynamic therapy (PDT) is limited by the tissue penetration depth of visible light. In contrast, traditional X-ray-induced photodynamic therapy (X-PDT) may cause collateral X-ray damage to healthy tissues. To address these challenges, this study presents an innovative heterojunction nanoplatform that produces reactive oxygen species (ROS) via dual photosensitizers upon soft X-ray excitation. The platform is built around a lanthanide-doped nanoscintillator core, NaLuF<sub>4</sub>:Tb/Gd(15 %/5 %)@NaYF<sub>4</sub> (SNPs), which efficiently converts absorbed soft X-ray energy into visible light. The porous structure of the porphyrin-based zirconium metal-organic framework (Zr-MOF) encapsulates carbon dots (CDs) as a photosensitizer, allowing for efficient fluorescence resonance energy transfer (FRET) from SNPs to CDs through nanoscale spatial confinement. Importantly, Zr-MOF itself acts as a secondary photosensitizer, synergizing with CDs to significantly enhance ROS production. In vitro and in vivo experiments demonstrate that under low-dose soft X-ray irradiation, this platform effectively penetrates 2 cm of tissue while “cascade-amplifying” ROS generation. This enhances oxidative stress within tumor cells, inducing mitochondrial dysfunction and DNA damage. The synergistic effects promote tumor cell apoptosis and suppress breast cancer growth, demonstrating high X-PDT efficacy and biosafety. This study not only highlights the potential of combining lanthanide scintillators with metal-organic frameworks (MOFs) and CDs, but also provides a novel, highly effective, and safe therapeutic strategy for breast cancer. It overcomes the tissue penetration limitations of PDT and significantly broadens the biomedical applicability of soft X-rays.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139802"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.jcis.2025.139803
Sara Chergaoui , Elena Tocci , Carmen Rizzuto , Giuseppe Prenesti , Damien P. Debecker , Tom Leyssens , Patricia Luis
Hypothesis
Crystal properties are essential in determining the functionality of final products in pharmaceutical and food applications. This study hypothesizes that membrane-assisted antisolvent crystallization (MAAC) can regulate supersaturation profiles to influence polymorph selection and crystal growth kinetics in glycine crystallization. By using polyvinylidene fluoride (PVDF) membranes to control ethanol diffusion, it is expected that MAAC can promote the formation of specific polymorphs, particularly α-glycine, through modulation of molecular self-assembly pathways.
Experiments
To test this hypothesis, MAAC was implemented with PVDF membranes to generate stable supersaturation conditions during glycine crystallization. The membrane served as a mass transfer barrier, enabling controlled ethanol diffusion and allowing for detailed analysis of crystal size and polymorphic distribution. Experimental crystallization outcomes were complemented by molecular dynamics (MD) simulations of glycine-water-ethanol systems at three supersaturation levels (S = 0.74, 1.35, and 2.39). These simulations were used to investigate the formation of molecular aggregates and hydrogen bonding patterns, and to quantify nucleation induction times under varying supersaturation conditions.
Findings
MAAC enabled the formation of α-glycine with a narrow chord length distribution and a mean size of 86 μm. MD simulations revealed that cyclic glycine dimers, precursors to α-glycine, formed at lower supersaturation, while disordered aggregates associated with β-glycine dominated at higher supersaturation. Ethanol was shown to modulate hydrogen bonding and self-assembly, influencing polymorphic outcomes. Induction times decreased significantly with increasing supersaturation, from 1.9 ns to less than 100 ps, highlighting the kinetic control enabled by membrane-regulated crystallization.
{"title":"Modulating crystal polymorphism via membrane-regulated supersaturation: an experimental and molecular dynamics simulation study","authors":"Sara Chergaoui , Elena Tocci , Carmen Rizzuto , Giuseppe Prenesti , Damien P. Debecker , Tom Leyssens , Patricia Luis","doi":"10.1016/j.jcis.2025.139803","DOIUrl":"10.1016/j.jcis.2025.139803","url":null,"abstract":"<div><h3>Hypothesis</h3><div>Crystal properties are essential in determining the functionality of final products in pharmaceutical and food applications. This study hypothesizes that membrane-assisted antisolvent crystallization (MAAC) can regulate supersaturation profiles to influence polymorph selection and crystal growth kinetics in glycine crystallization. By using polyvinylidene fluoride (PVDF) membranes to control ethanol diffusion, it is expected that MAAC can promote the formation of specific polymorphs, particularly α-glycine, through modulation of molecular self-assembly pathways.</div></div><div><h3>Experiments</h3><div>To test this hypothesis, MAAC was implemented with PVDF membranes to generate stable supersaturation conditions during glycine crystallization. The membrane served as a mass transfer barrier, enabling controlled ethanol diffusion and allowing for detailed analysis of crystal size and polymorphic distribution. Experimental crystallization outcomes were complemented by molecular dynamics (MD) simulations of glycine-water-ethanol systems at three supersaturation levels (S = 0.74, 1.35, and 2.39). These simulations were used to investigate the formation of molecular aggregates and hydrogen bonding patterns, and to quantify nucleation induction times under varying supersaturation conditions.</div></div><div><h3>Findings</h3><div>MAAC enabled the formation of α-glycine with a narrow chord length distribution and a mean size of 86 μm. MD simulations revealed that cyclic glycine dimers, precursors to α-glycine, formed at lower supersaturation, while disordered aggregates associated with β-glycine dominated at higher supersaturation. Ethanol was shown to modulate hydrogen bonding and self-assembly, influencing polymorphic outcomes. Induction times decreased significantly with increasing supersaturation, from 1.9 ns to less than 100 ps, highlighting the kinetic control enabled by membrane-regulated crystallization.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139803"},"PeriodicalIF":9.7,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hypothesis: The wetting behavior of a liquid drop on surfaces with varying hydrophilicity and hydrophobicity is crucial for fundamental research and practical applications. The conventional 90° contact angle threshold for distinguishing hydrophilic and hydrophobic surfaces has been debated.
Experiments: This study systematically investigates advancing contact angles and wetting transitions on polydopamine-coated NOA81 substrates patterned with regular arrays of square micro-pillars. By controlling both the intrinsic surface wettability and microstructured roughness, we explore how these factors influence wetting behavior.
Findings: The intrinsic advancing contact angles of the flat polydopamine-coated substrates () was tuned from 36.1° to 80.7°. Introducing square-pillar roughness substantially broadened the advancing contact angle (22° to 158°), revealing distinct roughness-dependent wetting behaviors for each . Two transition-capability regimes were identified: when > 80°, roughening enables a hydrophobic Wenzel-to-Cassie transition; while < 55°, increasing roughness induces a hydrophilic Wenzel-to-hemiwicking (penetrating) transition. These results demonstrate that the characteristic governs whether roughening activates hydrophobic or hydrophilic wetting pathways on square-pillar microstructured surfaces. The framework established here refines our understanding of roughness-mediated wetting transitions and provides practical guidance for designing microstructured surfaces with tailored wetting properties.
{"title":"Defining hydrophilicity and hydrophobicity through advancing contact angles and wetting transitions","authors":"Hsuan-Yi Peng , Kuan-Yu Yeh , Bang-Yan Liu , Li-Jen Chen","doi":"10.1016/j.jcis.2025.139801","DOIUrl":"10.1016/j.jcis.2025.139801","url":null,"abstract":"<div><div><em>Hypothesis:</em> The wetting behavior of a liquid drop on surfaces with varying hydrophilicity and hydrophobicity is crucial for fundamental research and practical applications. The conventional 90° contact angle threshold for distinguishing hydrophilic and hydrophobic surfaces has been debated.</div><div><em>Experiments:</em> This study systematically investigates advancing contact angles and wetting transitions on polydopamine-coated NOA81 substrates patterned with regular arrays of square micro-pillars. By controlling both the intrinsic surface wettability and microstructured roughness, we explore how these factors influence wetting behavior.</div><div><em>Findings:</em> The intrinsic advancing contact angles of the flat polydopamine-coated substrates (<span><math><msubsup><mi>θ</mi><mi>A</mi><mi>f</mi></msubsup></math></span>) was tuned from 36.1° to 80.7°. Introducing square-pillar roughness substantially broadened the advancing contact angle (22° to 158°), revealing distinct roughness-dependent wetting behaviors for each <span><math><msubsup><mi>θ</mi><mi>A</mi><mi>f</mi></msubsup></math></span>. Two transition-capability regimes were identified: when <span><math><msubsup><mi>θ</mi><mi>A</mi><mi>f</mi></msubsup></math></span> > 80°, roughening enables a hydrophobic Wenzel-to-Cassie transition; while <span><math><msubsup><mi>θ</mi><mi>A</mi><mi>f</mi></msubsup></math></span> < 55°, increasing roughness induces a hydrophilic Wenzel-to-hemiwicking (penetrating) transition. These results demonstrate that the characteristic <span><math><msubsup><mi>θ</mi><mi>A</mi><mi>f</mi></msubsup></math></span> governs whether roughening activates hydrophobic or hydrophilic wetting pathways on square-pillar microstructured surfaces. The framework established here refines our understanding of roughness-mediated wetting transitions and provides practical guidance for designing microstructured surfaces with tailored wetting properties.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139801"},"PeriodicalIF":9.7,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.jcis.2025.139799
Rong Gao , Xiaosong Wang , Guilan Fan , Yan Guo , Shoujun Guo , Chenhui Han , Junfang Ding , Yuliang Gao , Xiaojun Gu
Photoelectrochemical (PEC) N2 reduction reaction (NRR) using renewable solar energy enables the production of ammonia (NH3) from H2O as a hydrogen source under ambient conditions. However, the weak N2 adsorption and activation and the low light utilization efficiency lead to low NH3 yield. Herein, we investigate the effect of different Fe–O units on the photoelectrocatalytic ammonia synthesis using Fe-based metal-organic frameworks (MOFs), and modulate the conductivity of MOFs through the electronic interaction between graphene oxide (GO) and ligands to reduce the recombination of photogenerated carriers, thereby enhancing the PEC nitrogen reduction activity. Theoretical calculations suggest that the electron transfer from GO to MIL-88B via hydrogen bonding and the pathway from carbonyl oxygen in the ligand to metal‑oxygen clusters, improves the conductivity of the catalyst. Specially, the optimized MIL-88B/GO-8 photocathode exhibits an excellent NRR performance with maximum ammonia yield rate of 21.4 mg h−1 m−2 at −0.4 V and a Faraday efficiency of 9.7 % at −0.3 V. This work indicates that the efficient optoelectronics utilization through the synergism between MOFs and carbon-based conductive components in composite catalysts provides a potential for an efficient NRR under ambient conditions.
利用可再生太阳能的光电化学（PEC） N2还原反应（NRR）使H2O作为氢源在环境条件下生产氨（NH3）成为可能。但由于氮气吸附和活化较弱，光利用率低，导致NH3产率低。本文研究了不同Fe-O单元对fe基金属有机骨架（MOFs）光催化合成氨的影响，并通过氧化石墨烯（GO）与配体之间的电子相互作用来调节MOFs的电导率，以减少光生成载体的重组，从而提高PEC的氮还原活性。理论计算表明，电子通过氢键从氧化石墨烯转移到MIL-88B，以及从配体中的羰基氧到金属氧簇的途径，提高了催化剂的导电性。特别地，优化后的MIL-88B/GO-8光电阴极表现出优异的NRR性能，在- 0.4 V下，最大氨收率为21.4 mg h - 1 m - 2，在- 0.3 V下，法拉第效率为9.7%。这项工作表明，通过mof和复合催化剂中碳基导电组分之间的协同作用，有效地利用光电子学，为环境条件下的高效NRR提供了潜力。
{"title":"Efficient photoelectrocatalytic ammonia synthesis over graphene oxide-modified Fe-based metal-organic frameworks with high conductivity and photoresponsivity","authors":"Rong Gao , Xiaosong Wang , Guilan Fan , Yan Guo , Shoujun Guo , Chenhui Han , Junfang Ding , Yuliang Gao , Xiaojun Gu","doi":"10.1016/j.jcis.2025.139799","DOIUrl":"10.1016/j.jcis.2025.139799","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) N<sub>2</sub> reduction reaction (NRR) using renewable solar energy enables the production of ammonia (NH<sub>3</sub>) from H<sub>2</sub>O as a hydrogen source under ambient conditions. However, the weak N<sub>2</sub> adsorption and activation and the low light utilization efficiency lead to low NH<sub>3</sub> yield. Herein, we investigate the effect of different Fe–O units on the photoelectrocatalytic ammonia synthesis using Fe-based metal-organic frameworks (MOFs), and modulate the conductivity of MOFs through the electronic interaction between graphene oxide (GO) and ligands to reduce the recombination of photogenerated carriers, thereby enhancing the PEC nitrogen reduction activity. Theoretical calculations suggest that the electron transfer from GO to MIL-88B via hydrogen bonding and the pathway from carbonyl oxygen in the ligand to metal‑oxygen clusters, improves the conductivity of the catalyst. Specially, the optimized MIL-88B/GO-8 photocathode exhibits an excellent NRR performance with maximum ammonia yield rate of 21.4 mg h<sup>−1</sup> m<sup>−2</sup> at −0.4 V and a Faraday efficiency of 9.7 % at −0.3 V. This work indicates that the efficient optoelectronics utilization through the synergism between MOFs and carbon-based conductive components in composite catalysts provides a potential for an efficient NRR under ambient conditions.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139799"},"PeriodicalIF":9.7,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.jcis.2025.139798
Tainah Dorina Marforio , Andrea Carboni , Luca Mazzei , Sara Cascone , Lorenzo Lovatti , Edoardo Jun Mattioli , Francesco Valle , Matteo Di Giosia , Stefano Ciurli , Matteo Calvaresi
Carboranes are chemically and biologically stable boron‑carbon clusters with promising applications in medicinal chemistry. While their use in boron neutron capture therapy (BNCT) has been extensively explored, recent attention has shifted toward understanding their interactions with biological macromolecules, particularly proteins. Here, we characterize the interaction between closo-ortho-carborane and lysozyme (LSZ) using NMR spectroscopy, molecular docking and molecular dynamics simulations, and enzymatic assays. Experimental data demonstrate that carborane forms a stable 1:1 complex with LSZ (Carborane@LSZ), retaining the monomeric state and the protein fold, with only a limited number of amino acids involved in the interaction. In particular, NMR chemical shift perturbations revealed specific binding near the substrate-binding pocket, a result corroborated by molecular docking and molecular dynamic simulations. Carborane fits into a hydrophobic pocket near the substrate-binding site, where the recognition process is driven by hydrophobic interactions complemented by classical hydrogen and non-standard dihydrogen bonding. Carborane-@LSZ complex partially inhibits enzymatic activity (∼33 %). Extending this approach to bovine serum albumin (BSA) revealed similar binding principles, underscoring the generality of carborane–protein supramolecular interactions. These findings provide fundamental insights into pristine carboranes recognition by proteins and establish a foundation for designing carborane-based therapeutics and delivery platforms in nanomedicine.
{"title":"Structural determinants underlying the supramolecular binding between carborane and proteins in water","authors":"Tainah Dorina Marforio , Andrea Carboni , Luca Mazzei , Sara Cascone , Lorenzo Lovatti , Edoardo Jun Mattioli , Francesco Valle , Matteo Di Giosia , Stefano Ciurli , Matteo Calvaresi","doi":"10.1016/j.jcis.2025.139798","DOIUrl":"10.1016/j.jcis.2025.139798","url":null,"abstract":"<div><div>Carboranes are chemically and biologically stable boron‑carbon clusters with promising applications in medicinal chemistry. While their use in boron neutron capture therapy (BNCT) has been extensively explored, recent attention has shifted toward understanding their interactions with biological macromolecules, particularly proteins. Here, we characterize the interaction between <em>closo</em>-ortho-carborane and lysozyme (LSZ) using NMR spectroscopy, molecular docking and molecular dynamics simulations, and enzymatic assays. Experimental data demonstrate that carborane forms a stable 1:1 complex with LSZ (Carborane@LSZ), retaining the monomeric state and the protein fold, with only a limited number of amino acids involved in the interaction. In particular, NMR chemical shift perturbations revealed specific binding near the substrate-binding pocket, a result corroborated by molecular docking and molecular dynamic simulations. Carborane fits into a hydrophobic pocket near the substrate-binding site, where the recognition process is driven by hydrophobic interactions complemented by classical hydrogen and non-standard dihydrogen bonding. Carborane-@LSZ complex partially inhibits enzymatic activity (∼33 %). Extending this approach to bovine serum albumin (BSA) revealed similar binding principles, underscoring the generality of carborane–protein supramolecular interactions. These findings provide fundamental insights into pristine carboranes recognition by proteins and establish a foundation for designing carborane-based therapeutics and delivery platforms in nanomedicine.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"708 ","pages":"Article 139798"},"PeriodicalIF":9.7,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922805","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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